Methathesis polymerizable adducts of a divinylcyclohydrocarbon and cyclopentadiene

Abstract

An improved thermoset polymer having good mechanical properties and no detectable dicyclopentadiene odor is obtained by the ring-opening polymerization of a novel mixture of adducts comprising divinyl cyclohydrocarbon compound, such as 3,5-divinylcyclopentene and cyclopentadiene, optionally with added cycloolefinic compound, such as dicyclopentadiene, at polymerization conditions in the presence of an olefin metathesis catalyst.

What is claimed is: 
     
       1. A process for the polymerization under ring-opening polymerization conditions of a mixture comprising a major proportion of (1) adducts of a divinyl cyclohydrocarbon compound of up to 20 carbon atoms containing two vinyl groups as substituents on carbon atoms at least one carbon atom apart on an aliphatic ring system of from 5 to 10 carbon atoms and of 1 ring or 2 fused rings and cyclopentadiene, and (2) cyclopentadiene oligomers in the presence of an olefin methathesis catalyst system and, optionally, added dicyclopentadiene. 
     
     
       2. The process of claim 1 wherein the divinyl cyclohydrocarbon compound is of the formula ##STR5## wherein z is 0 or 1 and A individually is hydrogen, alkyl of from 1 to 4 carbon atoms inclusive, or the two A groups taken together form a second valence bond between the two carbon atoms to which they are attached or a divalent linking group of from 3 to 4 carbon atoms in the bridge and up to 1 carbon-carbon double bond. 
     
     
       3. The process of claim 2 wherein the catalyst system comprises a di(alkylphenoxy)tungsten halide, a triorganotin compound and, optionally, a boron halide. 
     
     
       4. The process of claim 3 wherein the tungsten halide is of the formula ##STR6## wherein R independently is alkyl of up to 10 carbon atoms inclusive, R' independently is hydrogen or R, R" independently is hydrogen or R, X is halo, x is 2 or 4 and y is 0 or 1 with the sum of x+2y being 4. 
     
     
       5. The process of claim 4 wherein the triorganotin halide is a trialkyltin halide wherein each alkyl independently has up to 10 carbon atoms. 
     
     
       6. The process of claim 5 wherein the divinyl cyclohydrocarbon is 1,3-divinylcyclopentane. 
     
     
       7. The process of claim 5 wherein the divinyl cyclohydrocarbon is 3,5-divinylcyclopentene. 
     
     
       8. The process of claim 5 wherein the divinylcyclohydrocarbon is 2,4-divinylbicyclo[3.3.0]oct-6-ene. 
     
     
       9. The process of claim 7 wherein the polymerization is carried out at a temperature from about 25° C. to about 200° C. 
     
     
       10. The process of claim 9 wherein the polymerization mixture contains at least about 60% total of adducts. 
     
     
       11. The process of claim 10 wherein the molar ratio of tungsten halide to tin hydride is from about 1:1 to about 1:15. 
     
     
       12. The process of claim 11 wherein X is chloro or bromo, R is alkyl of from 3 to 6 carbon atoms branched on the α-carbon atom, R' is R and R" is hydrogen. 
     
     
       13. The process of claim 12 wherein the tin hydride is a trialkyltin hydride in which each alkyl is straight-chain alkyl of from 3 to 6 carbon atoms inclusive. 
     
     
       14. The process of claim 13 wherein the boron halide promoter is present in an amount from about 0.05 mole to about 2 moles per mole of tungsten compound. 
     
     
       15. The process of claim 14 wherein the boron halide is boron trifluoride, the diethyl ether complex of boron trifluoride or the dibutyl ether complex of boron trifluoride. 
     
     
       16. The process of claim 13 wherein the tungsten halide is bis(2,6-diisopropylphenoxy)tungsten oxydichloride. 
     
     
       17. The process of claim 16 wherein the tin hydride is tributylin hydride. 
     
     
       18. The hard, infusible polymeric product produced by the process of claim 1. 
     
     
       19. The hard, infusible polymeric product produced by the process of claim 6. 
     
     
       20. A polymerizable mixture of (1) adducts of a divinyl cyclohydrocarbon compound of up to 20 carbon atoms, inclusive, containing two vinyl groups as substituents on carbon atoms at least one carbon atom apart on an aliphatic ring system of from 5 to 10 carbon atoms and 1 ring or 2 fused rings and cyclopentadiene, and (2) cyclopentadiene oligomers, optionally in the presence of dicyclopentadiene. 
     
     
       21. The mixture of claim 20 wherein the divinyl cyclohydrocarbon compound is of the formula ##STR7## wherein z is 0 or 1 and A individually is hydrogen, alkyl of from 1 to 4 carbon atoms inclusive, or the two A groups taken together form a second valence bond between the two carbon atoms to which they are attached or a divalent linking group of from 3 to 4 carbon atoms in the bridge and up to 1 carbon-carbon double bond. 
     
     
       22. The mixture of claim 21 wherein the divinyl cyclohydrocarbon compound is 3,5-divinylcyclopentene. 
     
     
       23. The mixture of claim 21 wherein the divinyl cyclohydrocarbon compound is 1,3-divinylcyclopentane. 
     
     
       24. The mixture of claim 21 wherein the divinyl cyclohydrocarbon is 2,4-divinylbicyclo[3.3.0]oct-6-ene. 
     
     
       25. A process for providing the adduct mixture of claim 20 comprising contacting the divinylcyclohydrocarbon and dicyclopentadiene at a temperature of at least about 160° C. and such that the molar ratio of divinylcyclohydrocarbon to dicyclopentadiene is from about 0.5 to about 2. 
     
     
       26. The process of claim 25 wherein the divinylcyclohydrocarbon is 3,5-divinylcyclopentene. 
     
     
       27. The process of claim 25 wherein the divinylcyclohydrocarbon is 1,3-divinylcyclopentane. 
     
     
       28. The process of claim 25 wherein the divinylcyclohydrocarbon is 2,4-divinylbicyclo[3.3.0]oct-6-ene.